Process for preparing alkylaminoketone oximes



Patented July 20, 1948 raoosss FOR PREPARING ALKY AMINO- KETONE OXliMESGlen H. Morey, Terre Haute, Ind., assignor to CommercialSolventsCorporation, Terre Haute, Ind, a corporation of Maryland No Drawing.

This invention relates to oximes of alkylamino- Alkylaminoacetone oximesin which the alkyl group is a lower alkyl member, are known and havebeen prepared by reacting chloroaceto-ne with lower alkylamine and thenreacting the product with hydroxylamine (Ben, 28, 2224, and Ben, 29,868).

I have now found the oximes of alkylaminoketones can be prepared breacting chloroketone oximes with alkylamines. The oximes in which thealkyl groups are derived from a higher fatty acid have been found topossess outstanding utility as cation active softeners, as described inmy copending application Serial No. 566,642, now United States PatentNo. 2,402,767. This property is entirely lacking in the lower members.prepared according to the process of my inVen tion.

The oximes of alkylaminoketones of my invention have the followinggeneral formula:

H H NOH R N-(%pJ- R wherein R is an alkyl radical having at least carbonatoms, R may be hydrogen or methyl and B may be methyl or ethylradicals,

Among the compounds included by the above formula there may be mentioneddecylaminoacetone oxime; undecylaminoacetone oxime; dodecylaminoacetoneoxime; tridecylacetone oxime; hexadecylaminoacetone oxime;octadecylaminoacetone oxime; dodecylaminomethylethylketone 0 xi m e;a(dodecylamino) ethylmethylketone oxime; a(dodecylamino)ethylethylketone oxime, and the like.

The chloro ketones which may be used in carrying out my inventioninclude the chlorinated compounds of acetone or dimethyl ketone; methylethyl ketone, and diethyl ketone.

In accordance with my invention, I carry out the reaction betweenehloroketone oxime and an alkylamine in an aqueous medium. And whenpreparing the higher alkyl compounds, the higher alkylamine ispreferably first converted to paste form to facilitate smooth reactionwith the chloroketone oxime. The higher alkylamine paste may be preparedby melting the alkylamine and if desired adding thereto a small amountof an emulsifying agent, for example, a small portion of some previouslyprepared alkylaminoketone Both higher and lower members maybeApplication December 4, 1944, Serial No. 566,641

3 Claims. (c1. zed-sec) oxime or any suitable emulsifying agent. Hotwater is then added to the melted amine and the mixture is stirredvigorously while cooling. If the paste tends to become thick whilecooling, a small portion of alcohol may be added to keep it fluid andproduce a more easily stirred, more homogeneous mass. The paste iscooled; for example, to room temperature (about 20-25 C.) and thechloroketone oxime, diluted, if desired, with alcohol to prevent caking'of the product, is added slowly or portionwise while stirringthoroughly. The product is 'a smooth white paste, readily dispersible inWater and possessing cationsoftening activity towards fabrics and thelike described in my copending application above referred to.

The product prepared as described above is in the form of itshydrochloride, and as such is readily utilizable as a cation-activesoftener material; r e

If it is desirable to isolate the product as the free amine, a largeexcess'of long chain alkylamine is usedover the stoichiometricequivalent to react with the chloroketone oxime, and this excess aminethen reacts with the chlorine to form'the chloride of the excess aminethus liberating the alkylaminochloroketone oxime as the amine. Or if theuse of a large excess of alkylamine is undesirable for any reason, thefree amine may be liberated by treatment with aqueous alkali.

In preparing the oximes of my invention the alkylamine and chloroketoneoxime may be reacted in substantially equimolecular Proportions.However, I prefer to utilize at least a small excess of amine in orderto insure substantially complete reaction of the chloroketone oxime.Otherwise, the reaction product has a tendency to darken due todecomposition or polymerization of the chloroketone oxime.

The amines which can be used to prepare the alkylaminoketone oximes ofmy invention include primary amines such as undecylamine, dodecylamine,tridecylamine, tetradecylamine, hexadecylamine, octadecylamine either asthe pure products or as mixtures of amines, such as the amines derivablefrom the higher fatty acids from coconut oil, from fish oils and thelike.

The product may be utilized in the form of its hydrochloride directly asformed, as described above, or it may be hydrolyzed to the free amine.However, I find it convenient to utilize the product in the form of thehydrochloride as in this form it has equally effective cation activeproperties as does the free amine.

The following examples further illustrate my invention.

Example I A quantity equal to 67 parts of octadecylamine was melted inareaction vessel. rii'small amount of octadecylaminoacetone ox imesuiiic'ient to serve as an emulsifying agent was dissolved in 250 partsof hot water and this was added to the melted octadecylamine. Thesolution was stirred vigorously and was allowed to coolwhi lie stirring.The small amount of octadecylam'inoacetone oxime caused the paste tomore homo-- geneous than it would otherwisehaue been. the paste hadcooled to about 45 C., 25 parts of ethyl alcohol was stirred in, and asa result, the paste became more fluid so that it could 'be stirred moreeasily and resulted in better homogeneity. The mixture was cooled toatmospheric temperature of about 25 C. then 30 parts of chloroacetoneaoxime, diluted with .25 parts oi alcohol was added portionwise whilestirring thoroughly. The resulting product was a smooth mite paste.

. Example I I w ven fr ers et a mixture or cr d lon chain aminesassaying approximately 84% Octadecyiamine, the remainder being largelyhexadecylam-ine, were melted with 209 parts of water, parts \Qf anemulsifying agent dissolved in 80 parts of water was added to the aminemixture which was then cooled while stirrin rapidly. Then l-Q parts ofalcohol were stirred in, aiid 30 parts of ch loroaeetone ioximedissolved in .20 .parts alcohol was added .por-tionwise to the aminepaste while stirring rapidly. When the paste was homogeneous thestirring was discontinued and the paste was in suitable form, as thehydrochlorides of the mixed oetadecyland hexadecylaminoacetone oximes,for use on suitable dilution as a textile softening material.

Ewample III Sixtyeseven parts of a mixture prepared by mixing C. .P.hexadecylamine and C. 'B. octadecylamine in the oporti n of (1.325%exadeeylm ne and 75% C- R iadesy amine were melted in a, reactionvessel. To the melted amine were added 20 parts of a 25% paste ofoctadecylaminoacetone oxime dispersed in 90 parts of water. The mixturewas allowed to cool and was stirred vigorously while cooling, resultingin a smooth paste. To the above paste was added portionwise a mixture of80 parts of .chloroacetoneoxime and 10 parts of alcohol while stirringand further cooling to room temperature of about 25 C. The mixtureresulted in a smooth paste which proved to be useful as a textilesoftener and had the advantage of not causing yellowing of the treatedtextiles.

While the above describes the preferred embodiments of my invention, itwill be understood that departures may be made therefrom within thescope of the specification and claims.

What is claimed is:

1. A process for preparing alkyl aminoketone oximes which comprisesreacting in an aqueous medium a chlorinated :lretoneoxinie of a leetoneselected from the group consisting of acetone, methylet'hylketone anddiethylketone with a primary alkyl amine.

2. A process for preparing alkylamin-oa-cetone oximes which comprisesreacting in an aqueous medium chloroacietone :oxime with a primary.alkylamine.

3. A :process for preparing octadecylaminoacetone oxime which comprisesreacting in an aqueous medium chloroacetone 'oxime with octadecylamin-e.

GLEN H. MOREY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number

